Kinetics of the carbothermal synthesis of Mo carbide catalyst supported on various semiconductor oxides

Molybdenum carbide synthesized by temperature-programmed carburization of MoO₃ supported on various semiconductor oxides (10 wt.% Mo) with a H₂/C₃H₈ mixture have been characterized and evaluated for Fischer-Tropsch synthesis. The carburization reaction appeared to be a 2-stage process involving formation of intermediate oxycarbide phase, which was further carburized to the metal carbide form. Both α-MoC_1 − x and β-MoC_1 − x phases were detected in all Mo carbide catalysts and MoO₃ was converted completely to molybdenum carbide during carburization. The carburization rate depended on the C₃H₈ composition in the feed and attained an optimum at a H₂:C₃H₈ ratio = 5 for all four supports (Al₂O₃, TiO₂, SiO₂, and ZrO₂). Carbide formation rate increased with Mo loading although it reached a ‘plateau’ at Mo loading beyond 15 wt.% Mo. The existence of a compensation effect and isokinetic relationship for both oxycarbide and carbide phases suggested that the conversion of Mo oxide to oxycarbide and oxycarbide to carbide phase was governed by the same topotactic mechanism. Mo carbide catalysts were evaluated for CO hydrogenation activity and Fischer-Tropsch specific reaction rate decreased in the order; MoC_1 − x/TiO₂ > MoC_1 − x/SiO₂ > MoC_1 − x/ZrO₂ > MoC_1 − x/Al₂O₃ parallel to the trend for Mo carbide production rate.     

Preparation of BaTiO3 nanopowders by the solution combustion method

Barium titanate was synthesized by the method of exothermal combustion in solutions using barium nitrate, titanium dioxide (TiO₂) and titanyl nitrate (TiO(NO₃)₂) as sources of titanium and barium and reducing agents such as glycine (C₂H₅NO₂), carbamide (СН₄N₂O) and glycerol (C₃H₅(OH)₃). In an effort to form a barium titanate phase, the materials synthesized using titanium dioxide were subjected to additional calcination at 800 °С. With titanyl nitrate the use of glycine and carbamide enabled carrying out a single-step synthesis of barium titanate. The obtained materials have pseudo-cubic lattice and are characterized by high stability of properties in a wide range of temperatures and frequencies of the electromagnetic field.     

The pyrolysis of individual plastics and a plastic mixture in a fixed bed reactor

Six thermoplastics, which represent more than two-thirds of all polymer production in western Europe, were pyrolysed in a static batch reactor in a nitrogen atmosphere. These were high density polyethylene (HDPE), low density polyethylene (LDPE), polystyrene (PS), polypropylene (PP), polyethylene terephthalate (PET) and polyvinyl chloride (PVC). The heating rate used was 25°C min⁻¹ to a final temperature of 700°C. These six plastics were then mixed together to simulate the plastic fraction of municipal solid waste found in Europe. The effect of mixing on the product yield and composition was examined. The results showed that the polymers studied did not react independently, but some interaction between samples was observed. The product yield for the mixture of plastics at 700°C was 9·63% gas, 75·11% oil, 2·87% char and 2·31% HCl. The gases identified were H₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈, C₄H₈, C₄H₁₀, CO₂ and CO. The composition of oils were determined using Fourier Transform infra-red spectrometry and size exclusion chromatography. Analysis showed the presence mainly of aliphatic compounds with small amounts of aromatic compounds. ©1997 SCI     

On adsorption and electro-oxidation of some compounds on tungsten carbide; their effect on hydrogen electro-oxidation

Adsorption and electro-oxidation of carbon monoxide, ethylene, acetylene, and hydrogen sulphide on tungsten carbide, in solutions of these compounds in 1 N H₂SO₄, have been investigated. It was found that CO, C₂H₄, and C₂H₂ do not undergo adsorption and oxidation and do not affect adsorption and electro-oxidation of hydrogen. H₂S does not oxidise as well, and it does not displace adsorbed hydrogen in any measurable amounts, though it does inhibit electro-oxidation of molecular hydrogen. Methanol is inert on tungsten carbide like carbon monoxide and hydrocarbons. Electro-oxidation of formaldehyde and formic acid proceeds without apparent WC-surface coverage by the adsorbed compound.     

Zinc oxide obtained by the solvothermal method with high sensitivity and selectivity to nitrogen dioxide

The effect of heat treatment using [Zn(H₂O)(O₂C₅H₇)₂] precursor ethylene glycol solution (synthesis temperature 125–185 °C, holding time 2–6 h) on the characteristics of the obtained nanocrystalline zinc oxide powder was studied. Under all synthesis conditions crystalline ZnO was formed with a wurtzite structure and an average crystallite size of 8–37 nm. The thermal behaviour and microstructure of the nanostructured ZnO powder were studied. The sensory properties of the obtained films in terms of the detection of hydrogen, methane, carbon monoxide and nitrogen dioxide were studied. The high sensitivity and selectivity of a thick ZnO film (synthesis temperature 145°С, holding time 6 h) when detecting NO₂ was established. It was found, that humidity had almost no effect on response value for NO₂ detection.     

Novel process for synthesizing fused mullite from titanium-rich medium/low grade or waste bauxite

This paper introduces a novel process to efficiently utilize medium-/low-grade or waste bauxite. The medium-/low-grade or waste bauxite is usually rich in iron oxide (total iron oxide content≥8%) or titanium dioxide (titanium dioxide content≥5%). In addition, both iron oxide and titanium dioxide have higher contents than typical bauxite (total iron oxide + titanium dioxide contents≥20%). It is difficult to obtain mullite with excellent properties using the process of beneficiation and sintering synthesis. Based on different reduction temperatures of K₂O, Na₂O, FeO_x, SiO₂ and TiO₂, the reduction of K₂O, Na₂O and FeO_x was set as the reduction end point. While SiO₂ start to be reduced, TiO₂ was unstable under high temperature and low oxygen partial pressure. The reason for the final formation of Ti₂O₃ in the TiO₂→TiO_2-x transformation process was analysed, and the morphology of the multiphase material obtained from the Ti₂O₃–3Al₂O₃·2SiO₂ solid solution was characterized. The reaction model was established.     

Iron(II) Sulfate(VI) from Titania Production as a Raw Material for Preparation of Hydrogen Sulfide Sorbents

A hybrid sorbent material for removal of hydrogen sulfide from air was developed. The material is based on activated carbon and iron compounds obtained from waste iron(II) sulfate(VI) heptahydrate. The iron salt is deposited on the carbonaceous support and subjected to oxidation (Fe²⁺ to Fe³⁺) using atmospheric oxygen under alkaline conditions. An effect of H₂O₂ addition to the process on the composition of the resultant material was also examined. X-ray diffraction (XRD) analyses confirmed easy conversion of waste FeSO₄·7H₂O to iron oxides Fe₃O₄ and FeOOH. The activated carbon supporting iron oxides revealed a higher efficiency in H₂S elimination from air compared to the commercial activated carbon, without any modification.     

A novel catalyst for the glycolysis of poly(ethylene terephthalate)

Poly(ethylene terephthalate) waste materials were depolymerized by ethylene glycol (EG), diethylene glycol (DEG), and propylene glycol (PG) in the presence of a novel catalytic system: titanium (IV)‐phosphate. The new catalyst was synthesized through a reaction of TiCl₄ with triethyl phosphate (C₂H₅O)₃P(O). It was found that the depolymerization of poly(ethylene terephthalate) fiber proceeds faster in the presence of titanium (IV)‐phosphate compared with compounds traditionally used in this process like Zn(OOCCH₃)₂. The oligomer distribution in the glycolysis products was studied by size‐exclusion chromatography. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1148–1152, 2003     

Titanium dioxide mediated photocatalyzed degradation of a textile dye derivative, acid orange 8, in aqueous suspensions

Titanium dioxide mediated photocatalysed degradation of a textile dye derivative, acid orange 8(1), was investigated in aqueous suspensions of titanium dioxide by monitoring the depletion of total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation kinetics were studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO₂ and in the presence of electron acceptors such as hydrogen peroxide (H₂O₂) and potassium bromate (KBrO₃) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient compared with other photocatalysts. The dye was found to be adsorbed on the surface of the photocatalyst at acidic pH.     

A novel route for synthesis of alumina–chromium carbide composites from PTFE-activated Cr2O3/Al/C combustion

Fabrication of alumina-chromium carbide composites was investigated by PTFE-activated Cr₂O₃/Al/C combustion synthesis. PTFE was employed as not only a reaction promoter, but a carburizing agent. Three reaction systems were prepared with different contents of carbon for the synthesis of Cr₂₃C₆, Cr₇C₃, and Cr₃C₂. The amounts of PTFE were selected to ensure combustion synthesis in the SHS (self-propagating high-temperature synthesis) mode and to provide carbon in quantities of 15 and 25?mol% of the total carbon. Experimental results showed that the combustion wave velocity and temperature decreased with increasing carbon, but increased with PTFE. A correlation between combustion wave velocity and temperature contributed to determination of the activation energy E_a =?89.15?kJ/mol for the combustion reaction. The increase of PTFE also improved formation of chromium carbides. As a result, the Cr₂₃C₆– and Cr₇C₃–Al₂O₃ composites were produced with almost no impurities. Due to a loss of carbon in carbothermic reduction, the Cr₃C₂–Al₂O₃ composite was obtained with Cr₇C₃ as the secondary carbide. SEM micrographs and DES analyses indicated that spherical carbide grains with a size of 0.5–3.0 μm were synthesized.     

Polyethylene terephthalate/low density polyethylene/titanium dioxide blend nanocomposites: Morphology,crystallinity, rheology,and transport properties

Physical features of polyethylene terephthalate (PET)/low density polyethylene (LDPE) immiscible blends, rich in PET, with and without titanium dioxide (TiO₂) nanoparticles are studied. These materials are of industrial interest, because they can be obtained by recycling PET bottles containing TiO₂ with their corresponding polyethylene made caps. Their potential application in packaging is investigated. Droplet-matrix morphology is observed by scanning electron microscopy; coalescence occurs during compression molding. Transmission electron microscopy results show that TiO₂ nanoparticles are located at the interface between PET and LDPE, forming a physical barrier that favors development of smaller droplets. Thermal analysis results are compatible with the morphology of the blends and the location of the TiO₂ nanoparticles. Viscosity obtained by extrusion continuous flow and oscillatory flow measurements in the linear regime show that some of the blends have viscoplastic behavior. Permeability results reveal that 80PET/20LDPE/TiO₂ blend nanocomposite shows a balanced barrier character to both oxygen and water vapor. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46986.     

The effect of processing conditions on carbon nanostructures formed on an iron-based catalyst

The carbon nanostructures formed during chemical vapour deposition (CVD) of ethene and hydrogen over an iron(III) oxide catalyst precursor have been investigated. Graphitic nanofibres and carbon nanotubes were both observed during synthesis, with the structures observed depending on the temperature and gas mix (C₂H₄ and H₂) used. Mixtures ranging from 100% to 5% ethene in hydrogen were investigated at different temperatures. During the synthesis, the iron(III) oxide was transformed into iron carbide (Fe₃C). The samples were characterised using transmission electron microscopy and X-ray diffraction. Filamentous nanostructures were observed with high hydrogen content (?80%) in the gas stream, whereas no filamentous structures were observed with ?20% H₂. The temperature of synthesis was varied between 500 and 800 °C, with higher temperatures giving higher carbon deposition rates, but also affected the nanostructures observed. However, it was found that increasing the temperature during CVD did not change the type of carbon deposited but did increase the deposition rate, providing a route to increase growth yields for a desired type of carbon nanostructure.     

CO2 reforming of waste plastics

Carbon dioxide reforming of polyethylene was carried out. Pyrolysis and catalytic carbon dioxide reforming were combined. Polyethylene was packed at the bottom of the reactor and the catalyst, Pd/Al₂O₃, was packed at the top of the reactor. The pyrolysis of the polyethylene occurred at the bottom of the reactor, and the pyrolysis products reacted with carbon dioxide on the catalyst bed. Carbon dioxide reforming occurred on the catalyst bed zone. Hydrogen, carbon monoxide, methane, ethane, ethene were produced at 910 and 720 K which were the catalyst and polyethylene temperature, respectively. Polyethylene was completely reformed to carbon monoxide and hydrogen when catalyst temperature was increased or polyethylene temperature was decreased.     

Simultaneous Synthesis and Densification of Titanium Oxycarbide, Ti(C,O), through Gas–Solid Combustion

The synthesis of titanium oxycarbide through a solid–gas combustion was investigated. Titanium powders containing TiC additive at levels ranging from 0 to 50 wt% were combusted in an atmosphere of carbon dioxide gas, at pressures ranging from 0.1 to 5.0 MPa. The characteristics of the synthesis process and the properties of the resulting product were found to depend on the level of the TiC additive and on the pressure of the carbon dioxide gas. Dense oxycarbides (∼96% relative density) with Vickers microhardness of ∼18 GPa were synthesized. In addition, the process presents a possible method for the fixation of carbon dioxide gas for the synthesis of useful materials.     

Water Gas Shift in Microreactors at Elevated Pressure: Platinum-Based Catalyst Systems and Pressure Effects

A new lab-scale microstructured reactor was used for investigations on enhancing the H₂/CO ratio in synthesis gas from biomass feedstocks via the water gas shift reaction. A model mixture of carbon monoxide, carbon dioxide, water, and hydrogen was used to reproduce the typical synthesis gas composition from dry biomass gasification. Catalyst layers were prepared and characterized; a combined incipient wetness impregnation and sol–gel technology was applied. The catalytic activities of Pt/CeO₂ and Pt/CeO₂/Al₂O₃ films were determined at temperatures of 400–600 °C and pressures of up to 45 bars. Increased pressure leads to higher values of CO conversion and to increased formation of hydrocarbons (CH₄, C₂H₆, etc.) and coke. Methane is the main by-product, and coke formation was attributed to the catalytic activity of peripheral reactor components.     

Semiconductor-mediated photocatalytic degradation of anazo dye, chrysoidine Y in aqueous suspensions

The photocatalytic degradation of an azo dye derivative, chrysoidine Y (1), was investigated in aqueous suspensions of titanium dioxide and zinc oxide by monitoring the change in substrate concentration employing UV spectroscopic analysis and decrease in total organic carbon content as a function of irradiation time under a variety of conditions. The degradation of the dye was studied under different conditions such as pH, catalyst concentration, substrate concentration and in the presence of electron acceptors such as hydrogen peroxide (H₂O₂) and potassium bromate (KBrO₃) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with zinc oxide     

Catalytic Steam Reforming of Fast Pyrolysis Bio‐Oil in Fixed Bed and Fluidized Bed Reactors

Catalytic steam reforming of bio‐oil is an economically‐feasible route which produces renewable hydrogen. The Ni/MgO‐La₂O₃‐Al₂O₃ catalyst was prepared with Ni as active agent, Al₂O₃ as support, and MgO and La₂O₃ as promoters. The experiments were conducted in fixed bed and fluidized bed reactors, respectively. Temperature, steam‐to‐carbon mole ratio (S/C), and liquid hourly space velocity (LHSV) were investigated with hydrogen yield as index. For the fluidized bed reactor, maximum hydrogen yield was obtained under temperatures 700–800 °C, S/C 15–20, LHSV 0.5–1.0 h^–1, and the maximum H₂ yield was 75.88 %. The carbon deposition content obtained from the fluidized bed was lower than that from the fixed bed. The maximum H₂ yield obtained in the fluidized bed was 7 % higher than that of the fixed bed. The carbon deposition contents obtained from the fluidized bed was lower than that of the fixed bed at the same reaction temperature.     

Study of the preparation of bulk tungsten carbide catalysts with C2H6/H2 and C2H4/H2 carburizing mixtures

The influence of the preparation procedure of tungsten carbide on the mechanism of carburization is discussed. This work is focused on the reduction and the carburization of tungsten trioxide by a mixture of hydrocarbon and H₂ to form WC. Temperature-programmed reaction spectra obtained with CH₄, C₂H₆ and C₂H₄ have been measured. In presence of the CH₄-H₂ mixture, H₂ is the reducing agent and the hydrocarbon is consumed for the carburization whereas C₂H₆ or C₂H₄ participates in the reduction of the tungsten oxide. The temperatures of reduction and carburization are lower by about 150 K using C₂H₆ or C₂H₄ instead of CH₄. Such a decrease of the temperature of reduction of tungsten oxide is needed to avoid the formation of poorly reducible compounds that can occur during the preparation of supported tungsten carbide. Furthermore, the surface area of the resulting carbide is 25 m²/g with C₂H₆ and C₂H₄ and 10 m²/g with CH₄. During the carburization, the deposit of excess carbon on the WC surface is larger with the C₂ hydrocarbons than with CH₄, but it protects the carbide and can be removed by hydrogen treatment. This revised version was published online in July 2006 with corrections to the Cover Date.     

Combined Steam Reforming of Methane and Fischer–Tropsch Synthesis for the Formation of Hydrocarbons: A Proof of Concept Study

Higher alcohol synthesis over a K₂O-promoted Co₂O₃/CuO/ZnO/Al₂O₃ catalyst has been studied in an internal recycle reactor under steady-state conditions using hydrogen to carbon monoxide inlet ratios between 0.5 and 3.3 and inlet carbon dioxide concentrations between 0 and 10%. The selectivity of hydrocarbons and alcohols with 1-8 carbon atoms was obtained as a function of exit carbon dioxide content, exit hydrogen to carbon monoxide ratio, and operating temperature (498-578 K), using space velocities between 1500 and 15 000 h^-1 (STP). These experiments, combined with information obtained from active catalyst characterization using XPS, indicated that the chain growth probability factor of higher alcohols was independent of conversion, whereas that of hydrocarbons was dependent on conversion.     

Irradiation Grafted Polymeric Films. II. Gas Transport Properties of Hydrated Potassium Acrylate-Grafted Polyethylene Films

Abstract

The permeability constants of oxygen and carbon dioxide through hydrated potassium acrylate-grafted polyethylene films increase rapidly as the degree of hydration of the films increases above about 28 wt %. Below about 28 wt %, the carbon dioxide permeability constant increases with the degree of hydration. In the case of oxygen, the opposite is true.

The separation factor (CO₂/O₂) increases rapidly with film hydration up to about 28 wt %. Above this degree of hydration, the separation factor gradually approaches the value for pure water. An explanation for the results obtained is presented.